Lather producing composition



Oct. 13, 1953 J. G. SPITZER ET AL 2,655,480

LATHER PRODUCING COMPOSITION- Filed Nov. 2, 1949 NORMA/V F/A/E INVEN T0125 Y I M M ,shrfi ram ATTORNEYS Patented Oct. 13, 1953 UNlTE seas ears r orricr:

LATHER PRODUCING COIVIPOSITION Spitzer Application November 2, 1949, Serial No. 125,032

This invention relates to a composition for use in producing a soap or detergent lather without resorting to any manual or mechanical whipping or agitating operation.

Prior to the present invention, preparations employed to produce lather for shaving, shampooing or other washing or cleansing operations, have included soaps in solid, powdered, liquid or cream form, which are whipped up into a lather by agitation, sometimes with the aid-oi a brush or other whipping device, as in preparing shaving lather, sometimes by agitation with the hands, as in shampooing, and sometimes by agitation by water in preparing the lather for other washing operations. For example, preparations employed to prepare the beard and skin for shaving have generally included lathering soaps and brushless creams. Lathering soaps in various forms are whipped up into a lather with water on the face, or in a cup or bowl, by means of a brush. This lathering operation is time-consuming and somewhat inconvenient, and the brushless creams were introduced to obviate the shortcomings of the lathering operation.

Brushiess creams are typica lymodified vanishin creams that are spread upon the face in the state that they are sold without forming any lather. They are somewhat greasy or salve-like in texture and are quite adherent to the skin.

. They also adhere to other surfaces and for this reason tend to clog razors and to cause or promote the clogging of drains. The heavy texture or high viscosity of brushless creams makes them generally less desirable than the light and more readily removable soap lathers, particularly in that the creams do not permit as close or satisfactory shaves as the lathers and unless very thoroughly rinsed ofl, leave a greasy or sticky feeling on the skin.

In shampooing the hair, soap solutions are generally applied to the hair and then worked into a lather with the hands. The working up of lather delays the actual hair washing opera.- tion and the rubbing of the hair and scalp incident to mechanically working up the lather may be undesirable in some cases.

The present invention has for its object the provision of an improved composition for forming soap or synthetic detergent lather of fine quality without the use of a brush or any mechanical whipping mechanism or operation. The composition of the present invention provides a lather, such as a shaving, shampooing or washing lather, that is formed as the compositlon is released from its container and may be 21 Claims. (01. 252-) 2 directly applied to the skin, hair, or other part or material in lather form without the use of a brush or other applying instrument and without preliminary mechanical or manual lather forming operations.

In general, the above and other objects of the invention are carried out by employing a composition comprising a water solution of a suitable soap or like detergent and a highly volatile organic liquid, hereinafter generally termed a propellant. At least a substantial proportion of the propellant used in the mixture is insoluble in the soap solution and the two primary ingredients are mixed and maintained under sufllcient pressure so that the insoluble portion of the propellant is in liquid phase. existing as droplets or in the form of a liquid-liquid emulsion in the soap solution. The mixed primary ingredients are confined at the vapor pressure of the propellant in a pressure-tight container having an opening controlled by a suitable manually operable valve. When the valve is opened, the pressure on the composition is released as it emerges from the container, with the result that a fine textured creamy lather is produced. The action is apparently such that the volatile propellant liquid, entrapped as an emulsion within the liquid soap solution, vaporizes upon the release of pressure therefrom, forming fine gas cells throughout the liquid soap solution and thus forming it into a lather.

In describing the invention in detail, reference will be made to the accompanying drawing, in which the single figure 1s a sectional elevation representing a can or container suitable for packaging our improved composition and provided with an outlet valve.

T-e nature of the soap or detergent used, n1 .ii jh not critical, has an efiect on the type oer produced. Suitable soaps include the 11 steal-ate soaps, such as he potassium, onium and soluble amine soaps oi commernzraric acid, particularly the trlethanolamine rpholine soaps oi commercial stearic acid. 'i'lr product sold commercially as stearic acid t i ;t'ually a mixture consisting primarily of s aearic and palmitic acids. We shall use the torn: stearates" herein to designate soaps of c m: -.ricrcial stearic acid, although soaps of chemizznl pure stearic acid would be the equivalent for We purposes of this invention. The stearates may be made by neutralization of stearic acid with suitable alkali, or may be introduced in the form of animal fats, such as taliow, which are rich in stcaric acid and which, when saponifled,

3 form soaps rich in stearic acid. Mixtures of the various stearate soaps may be used, and small proportions, preferably less than per cent, of a less soluble soap, such as a sodium stearate soap may be used with the more soluble stearate soaps mentioned above to secure the desired consistency, particularly when the product is used toproduce a shaving lather. Vegetable oil soaps, including the soaps of cocoanut oil, cottonseed oil, olive oil, soya oil, etc., may be used either alone or in admixture with the soluble stearate soaps. when the vegetable oil soaps are used alone, or as the primary soap ingredient, the resultant lather is somewhat looser, coarser and less stable than when soluble stearate soaps or mixtures including a substantial proportion thereof are employed. For this reason, when the composition is to be used for producing shaving lather, a substantial proportion of soluble stearate soap is used, whereas compositions producing shampoo or washing lathers preferably comprise or contain a substantial proportion of vegetable oil soaps. On the other hand, vegetable oil soaps may to advantage be used in admixture with soluble stearic acid soaps to prepare a shaving lather producing product for the purpose of making the soap solution less l' aely to gel at low temperatures than solutions made from the stearate soaps alone. In preparing our product for producing shaving lather, We use ll upwards of per cent, preferably from 60 to 100 per cent, of soluble stearate soap, the balance, if any, being an ordinary vegetable oil soap or animal fat soap, which is partially composed of stearate. Preferable soaps are triethanolamine,

morpholine and potassium soaps, although ammonium soaps are usuable but have an undesirable odor.

When the product is employed to produce a relatively loose or coarse lather more suitable for shampooing or other washing than for shaving, the soap solution may be formed of vegetable oil soaps, examples of which have been referred to above, and of which cocoanut oil soaps are excellent examples. Certain synthetic surface-active agents, usually called wetting agents, may also be used as the soap ingredient. The wettin agents so employed should be anionic or nonionic in character. They should be appreciably soluble in water and of the type that foam in water solution. Examples of such agents are triethanolamine lauryl sulfate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, and water soluble polyoxyethylene ethers of alkyl substituted phenols.

Although not essential to the invention, it may in some cases be desirable to add small proportions of the above-described anionic or non-ionic wetting agents to our lather-forming composition including other soap solutions, for the purpose of avoiding an oily residue on the skin and in order to facilitate rinsing off the lather. When thus added to another soap solution, the wetting agents should be used in relatively small proportions, preferably from about /2 per cent to about 5 or 6 per cent by weight in the soap solution.

The amount of soap employed to form the aqueous soap solution of our composition is not critical and generally depends upon the nature of the soap used. The low limit is the minimum amount that gives a satisfactory lather and the upper limit is fixed either by economic considerations or by the amount which will form a gel at the lowest temperatures likely to be encountered in use. A preferred range for all soaps is from about 5 to about 18 per cent by weight of the soap and water solution. With the soluble amine stearate soaps, the maximum range of usable soap concentration is between about 2 per cent and 30 per cent by weight if the soap is entirely or substantially composed of triethanolamine stearate. If the soap is potassium stearate, the useful range is somewhat narrower, bein from about 5 to 20 per cent. When vegetable soap is used as a part of the soap mixture, the lower and upper concentration limits are raised somewhat and may be from about 5 to about per cent by weight of the solution.

The following are examples of soap solutions useful in preparing our composition, the amounts being given in per cent by weight of the soap and water solution. As is customary, we generally prefer to add a small percentage of glycerine to our soap solutions for use in compositions that produce shaving lather. The glycerine is added for the known purpose of slightly increasing the stability of the lather. About 5 per cent by weight of glycerine based on the soap solution is a suitable proportion but the amount is not critical. When used, the glycerine is substituted for a part of the water in the soap solution and it may be added to each of the following examples by reducin the proportion of water indicated by an amount equal to the proportion of glycerine added.

Per cent 1. Triethanolamine stearate 8.0

Triethanolamine soap of cocoanut oil fatty acids 2.0 Water 9 .0 2. Triethanolamine stearate 10.0 Water 90.0 3. Triethanolamine stearate .0 Water 97.0 4. Potassium stearate 10.0 Water 90.0 5. Morpholine stearate 10.0

Water 90.0 6. Triethanolamine stearate 5.0

Triethanolamine soap of castor oil fatty acids 5.0 Water 90. 7. Triethanolamine stearate 3.3

Triethanolamine soap of cocoanut oil fatty acids 6.7 Water 90.0 8. Triethanolamine soap of castor oil fatty acids 10.0 Water 90.0 9. Triethanolamine soap of soya oil fatty acids 10.0

Water 90.0 10. Triethanolamine stearate 8.0 Sodium stearate 2.0 Water 90.0 11. Triethanolamine oleate 10.0 Water 90.0 12. Triethanolamine stearate 10.0 Triethanolamine oleate 10.0 Water 80.0 13. Sodium lauryl sulfate 10.0 Water 90.0 14. Triethanolamine lauryl sulfate 10.0 Water 90.0 15. Sodium alkylbenzene sulionate 10.0 Water 90.0 16. Polyoxyethylene ether of 'alkyl substituted phenol 10.0 Water 90.0

e I 0 a J.

8,865,4560 6 6 Percent carbons oi the proper vapor pressure range. Ex- 17. Triethanolamine stearate 10.0 amples of these propellants are:

sd1um lauryl sulfate 1,2 dichlor l,1,2,2 tetrafluorethane(CClFa.CClFa)- Water I Trichlortrifiuorethane (CzChFa). 18. Triethanolamine stearate 10.0

Dichlordifluormethane (CChFs). Polyoxyethylene ether of substi' Monochlordifluormethane (CHClFz).

tuted phenol Monofluortrichlormethane (CFCla). water 1,1 difluorethane (CI-I3.CHF2). Tflethimmmme steam" 1 monochlor 1,1 Difluorethane (cclracrm.

Triethanolamine soap or cocoanut oil iatty acids 3,3 As to these compounds, absence of tingling sen- Triethanolamine 1 l sulfate 5,4 sation combined with production of the best Water 34,6 shaving lather consistency is achieved by using Generally speaking, the propellant ingredient of our invention is a volatile organic material that exists as a gas at ordinary room temperatures, exists largely as a liquid at elevated pressures practically maintainable in suitable containers for our composition and that has a low solubility in water. The propellant must be of such nature that it does not destroy the lather or decompose the lather-producing soap in solution.

We have discovered that relatively insoluble saturated aliphatic hydrocarbons and relatively insoluble partially fluorinated and partially or wholly chlorfiuorinated hydrocarbons having vapor pressures within the range from about 5 to about 300 pounds per square inch gauge, and preferably from about 30 to 80 pounds per square inch gauge at 70 F., possess these properties. The propellant may be formed of a mixture of two or more such compounds which, although the individual ingredients may have vapor pressure outside the desired range, have, when combined, a vapor pressure within that range. The water solubility of the propellant or propellant mixtures should be such that they exist mainly as a. liquid phase undissolved in the soap solution when the two are mixed under pressure sufilcient to maintain the propellant in the liquid phase.

Particularly when the product is used to produce shaving lather, it may be desirable to avoid the use of propellants that result in a marked tingling or burning sensation when the composition is applied to the skin. We have found that the useful lather-producing propellants are generally those with very low solubility in water. The propellant should have a solubility such that less than about 32 cc. of the propellant gas will dissolve in 100 grams of water at one atmosphere absolute pressure and about 25 C. The best propellants have a solubility 01' less than about 10 cc.

of gas in 100 grams of water at the stated pressure and temperature. In general, the least soluble propellants produce little or no burning sensation on the skin, particularly if hydrocarbons in which the hydrogen atoms are substituted by chlorine atoms alone or by more chlorine atoms than fluorine atoms are avoided. We have discovered that the straight chain saturated aliphatic hydrocarbons of suitable vapor pressure, which comprise propane, butane. sobutane and cyclobutane are suitable lather-forming propellants and do not cause an undesirable burning sensation. The inflammability 01' these propellants introduces a flre hazard. Also usable, particularly in admixture with other propellants. are the saturated, partially but not completely fluorine substituted aliphatic hydrocarbons oi suitable vapor pressure, such as 1,1 difluorethane CI-ImCHFz), which causes little tingling or the skin. The most desirable propellants xor lather forming compositions are the substantially we tar insoluble chlorine and fluorine substitu ed hyd sothose propellants in which all of the hydrogen atoms are replaced by chlorine and fluorine and in which the number oi. fluorine atoms equals or exceeds the number of chlorine atoms, asis true, 1or example, oi dichlordiiluormethane, 1.2 dichlor l,1,2,2, tetrafluorethane and trichlortrifiuorethane.

Mixtures of difierentpropellant compounds are useful for providing the particular vapor pressure desired, and propellants comprising mixtures of dichlordifluormethane and 1,2 dichlor l,l,2,2 tetrafluorethane, of monofluortrichlormethane and dichlordifluormethane and of trichlortrifluorethane and dichlordifluormethane are satisfactory for this purpose. For example, dichlordifluormethane, which has a vapor pressure 01' about pounds per square inch gauge and 1,2 dichlor l,1,2,2 tetrafluormethane, with a vapor pressure of about 13 pounds per square inch gaug at 70 F., may be mixed in various proportions to form a propellant having an intermediate vapor pressure which is well suited for use in relatively inexpensive containers.

As stated, the fluorinated chlorinated hydrocarbons in which all of the hydrogen atoms are replaced by chlorine and fluorine and in which the number of fluorine atoms in the molecule equals or exceeds the number of chlorine atoms. are particularly desirable. They have low solubilities-onlya few cubic centimeters of the gas being soluble per grams of water at room temperature and one atmosphere pressure, and we believe this low solubility is significant in accounting for their good performance. The fluorinated chlorinated propellant compounds which do not meet the foregoing requirement as to hydrogen atom substitution are definitely less desirable. This is true of monoohlordifiuormethano, which has one unreplaced hydrogen atom in the molecule. Similarly, 1 monochlor 1,1 difluorethane, which has three unreplaced hydrogen atoms in the molecule. is a less desirable propellant. So also is monofluortrichlormethane, which has more chlorine than fluorine atoms in the molecule. All of these less desirable propel-' lants cause undesirable smarting of the skin." Furthermore, they form less stable lathers than the previously described preferred propellants. However, they maybe used in admixture with the more desirable propellants, in which case their undesirable effects are less evident.

We have found that the'unsaturated aliphatic hydrocarbons, the chlorinated hydrocarbons containing no fluorine, and the completely fluorinated hydrocarbons as well as the volatile ethers do not form stable lathers or lathers of useful consistency. All of these except the completely fluorinated hydrocarbons produce a marked burning or smarting sensation on the skin. The completely fluorinated hydrocarbons do not smart strongly butdo not form satisfactory lathers, Inca when the pressure is released from, mixtures assessoof these compounds and soap solutions, the gas eiscapes at once, leaving a watery liquid soap solut on.

When it is desired to use a propellant having a relatively high vapor pressure in inexpensive can type containers, we have found that the vapor pressure can be reduced without the use of low vapor pressure propellants and without destruction of the lather-producing properties of the composition by adding a minor proportion of a suitable petroleum oil fraction. Petroleum oils of the pure refined industrial white oil type, starting with deodorized kerosene which has a density of about 0.78 at 60 F. and a viscosity of 30 to 35 seconds Saybolt at 100 F. and running up to a light mineral oil having a density of 0.84 at 60 F. and a viscosity of 65-75 seconds Saybolt at 100 F. or h her, may be added in proportions to give the desired low vapor pressure without destroying the lather-producing properties of the comppaition. Petroleum fractions of lower boiling point than kerosene are undesirable since they have an adverse effect on the quality of the lather, whereas white oils within the indicated range produce an excellent lather when employed in our composition, despite the fact that the incorporation of such oils in ordinary soap solutions makes it practically impossible to work the soap into a lather by the use of a brush.

The amount of oil added is selected in accordance with the desired reduction in vapor pressure but is limited by the amount which will adversely afiiect the quality of the lather produced. We have found that the maximum permissible quantity of oil varies with its viscosity. Thus, whereas up to about 20 per cent of oil based on the soap solution may be used with the oil having a viscosity of more than about 40 seconds Saybolt at 100 F., when oils in the viscosity range between -30 and-40 seconds Saybolt at 100 F. are employed,

the maximum amount that will not impair the lather quality isnpproximately per cent. It is generally preferred, when oil is added, that the soap in the soap solution comprise more than 60 per cent stearate soap. when mineral oil is added to compositions containing a major proportion of vegetable oil soaps, the lather is generally of inferior quality. When oil is added, the use of sodium salts and sodium salt wetting agents should be avoided, and at least 10 per cent of soap should be employed in the soap solution. Examples of our modified composition in which oil is employed to reduce the vapor pressure are given hereinafter.

The amount of propellant used in the soap solution and propellant composition of our invention is not critical, but is determinative of the density of the lather produced. The greater the proportion of propellant, the lower will be the density of the lather. In general, useful lather densities lie in the range of about .02 gram per cc. up. Lathcrs of such low density as .02 or .03 gram per cc. are

rather firm and dry to the feel. At densities above about 0.20 gram per cc., lathers flow readily and hence are less desirable for shaving purposes but are useful for other washing operations, such as shampoolng. Shaving lather densities should lie between about .03 and .25 gram per cc., while for shampooing or other uses a wider range of densities may be used. The preferred range for 8 percentage by weight of propellant required to produce a given lather density varies with the molecular weight of the propellant used. When using a propellant mixture comprising 39 per cent by weight of dichlordifluormethane and 61 per cent of 1,2 dichlor 1.1.2.2 tetrailuorethane, the proportion of propellant by weight of the composition ranges from about 23.3% to about 3.17% for lather densities of about .03 to about .25 gram per cc. This propellant mixture has a molecular weight of about 151. Any desired density with any chosen propellant or propellant mixture can be approximated from the formula 100M D- (at F.) where D is the density in grams per cc., M is the molecular weight of the propellant, and X is the piercent by weight of propellant in the composi- Thus the proportions of propellant in terms of moles per grams of the propellant and soap composition within the useful range of lather densities given above (.02 to .25 gram per co.) may be calculated by solving for X in the abovestated formula and dividing the-obtained value of X by the molecular weight of the selected propellant. For example, with D=.02, X will equal .2041 M for any given propellant; hence the proportion of propellant in terms of moles per 100 grams of the composition will be about .20 mole. With D=.25, X will equal .0125 M, or .0125 mole per 100 grams of the composition.

Our composition is preferably enclosed in a container from which it is propelled as needed by the propellant gas pressure in the head space of the container. As the amount of liquid composition in the container decreases, the concentration of propellant in the liquid mixture drops due to the fact that some of the propellant evaporates to fill the increased head space. Thus, the density of the lather increases as the contents of the container decreases. For this reason, we prefer to use such a proportion of propellant to soap solution that the initial lather density when the container is substantially full lies under about 0.15 gram per cc., where the composition is to produce shaving lather. If the initial lather density is below about 0.06 gram per cc., the fin lather will be dry and uneven.

The vapor pressure of the propellant at normal room temperatures determines the rapidity with which the lather is formed when the pressure on it is reduced to atmospheric pressure. To insure that the product will be expelled from the container, the vapor pressure of the propellant must be greater than 15 pounds per square inch absolute at room temperature. When propellants of slightly higher vapor pressure are used, the composition when released from the pressure container emerges as a liquid which thereafter swells to a lather. Thus, with propellants having vapor pres; sures of about 5 to 15 pounds per square inch gauge at 70 F., the product emerges as a liquid or r. semi-liquid and is suitable for a shampoo since it swells into a lather after emergence. Compositions including propellants of such low vapor pressure can be used to produce shaving lathers, but it is preferred to employ higher pressure propellants for this purpose so that the composition emerges as a substantially fully developed lather when released from the container. Propellants having vapor pressures of about 25 pounds persquarc inch gauge or more at 70 I". give products that emerg as lothcrs when re- 3 113 atmospheric uro et norlnal mom g temperatures. Propellants having lower vapor" pressures in the range from to 25 pounds per square inch gauge at 70 F. produce products that emerge as lathers at elevated temperatures. but

' at temperatures below about 70 F. emerge as liquids that slowly swell to lathers.

The upper limit of the propellant vapor pressure is not critical and is determined by considerations of safety and economy. Depending on the type or container used, pressures from about 5 to pounds per square inch gauge up at 70 F. can be employed for shaving lathers, but with mass produced inexpensive containers of the type used for beer cans, the maximum propellant vapor pressure should not exceed about 60 pounds per square inch gauge at the indicated temperature. Further, the higher the vapor pressure or the propellant, the greater is the proportion thereof required to fill the head space in the can as the liquid content is withdrawn. A practical range of propellant vapor pressures when using can type mass produced containers lies between about 5 to 65 pounds per square inch gauge at 70 F. and for shaving lather producing compositions should preferably be between about and 65 pounds per square inch gauge at that temperature.

The following are examples of our composition. the percentages of ingredients being given by weight. It is to be understood that the composition is confined under the vapor pressure of the propellant at the prevailing temperature until lather is required. whereupon a suitable portion of the composition is released to atmospheric pressure and emerges as the lather or a latherproducing liquid. The following compositions that are designated shaving lather producing compositions emerge as stable lathers when released to atmospheric pressure at normal room temperatures:

Shaving lather producing compositions Percent A. Soap solution 1. 2, 5, 12. 17, 18. 4, 7. 19

Or 3 93.33 Dichlordifluormethane 2.6 1.2 dichlor 1.1.2.2, tetraiiuorethane-.. 4.07 B. Soap solution 2 or 4 86.3 Dichlcrdifiuormethane 0.0 45 sec. visc. mineral oil 7.7 C. Soap solution 1 83.7 Dlchlordifluormethane 9.6 65/75 sec. visc. mineral 011.----. 6.7 D. Soap solution 1 88.5

Dichlordifiuormethane 8.4 /35 sec. vise. kerosene 3.1 E. Soap solution 2 94.7 Dichlordifluormethane 5.3 F. Soap solution 2 .4 90.1 1,2 dichlor 1.1.2.2. tetrailuorethane 6.6 Monofluortrichlormethane 3.3 G. Soap solution 2 93.8 Dichlordifiuormethane 3.2 Trichlortrifiuorethane 3.0 H. Soap solution 1 84.0 Diiluorethane 3.3 1.2 dichlor 1.1,2,2 tetrafiuorethane 2.7 I. Soap solution 2 94.5 Dichlordifluormethane 2.1 Monofluortrichlormethane 3.4 J. Soap solution 2 l 97.7 Butane 2.3 K. Soap solution 2 97.43 Isobutane 2.57 L. Soap solution 2 97.8

Propane J; 33

Shampoo and other lather producing compositions Percent M. Soap solution 7, 8, 13. 14. 15 or 18 93.33

Dichlordifluormethane 2.6 1.2 dichlor 1.1.2.2 -tetrafluorethane 4.07 N; Soap solution 2 "as--- 94.6 Diohlordifluormethane 5.4 O. Soap solution 2-..; 90.9

Diehlordifluormethane 3.55 1.2 dichlor 1.1.2.2 tetrafluorethane.. 5.55

It is preferred to enclose our composition in a pressure-tight container such as that shown in the drawing. The container shown is a can having a body portion 1 and a suitably attached concave bottom wall 2. An outlet valve is suitably secured in an opening in the top wall of the can. The valve shown comprises a tube 3 havifig an inturned flange 6 at its inner end which forms a valve seat. A valve plug 5 carried by a valve stem 8 is resiliently held in engagement with the seat 4 by a spring I which is compressed between the flange 6 and a stop 5 struck from the stem 0. A nozzle 0 is secured to the upper end of the tube 3 and extends laterally from the tube. The stem 0 extends through an opening in the nozzle and is provided with a push button It which may be depressed to open the valve. A tube i l of suitable material is fitted over the tube 3 within the can and extends in a point near the juncture of the side-and bottom walls I and 2 of the can substantially in line with the nozzle 9 in order to insure expulsion of substantially all 01' the can contents when the can is tilted in the direction of the nozzle.

The container is filled with the desired composition oi soap solution and propellant in the proportions explained. The soap solution and propellant ingredients of the composition may be separately or simultaneously introduced. The composition or the propellant ingredient thereor is preferably introduced under a pressure above its vapor pressure at the prevailing temperature so that the propellant is in liquid phase except for the small amount in gaseous phase that fllls the head space. The composition is mixed in the container by agitation induced by shaking, or by the introduction 01 the ingredients, and when a lather is required, the valve is opened by depressing the button 10. whereupon the lather or lather-forming composition emerges from the nozzle 8.

The term soap solution as used herein and in the appended claims is inclusive of solutions in which the soap ingredient or the major proportion thereof comprises the soluble foaming wetting agents described above. examples or which are included in the above-listed examples oi soap solutions.

We claim:

1. A package comprising a pressure-tight container having a valve-controlled opening and containing a composition for use in producing a. stable lather consisting essentially oi a liquid mixture 01' an aqueous soap solution and 9. vols.- tile propellant in liquid phase, the composition being confined in the container under the vapor pressure 01' the propellant. said soap solution comprising a solution which is non-gelling at room temperatures and which contains at least about 5% and not substantially exceeding about 30% by weight oisoap. said propellant being a halogenated alkane having not more than two carbon atoms and containin at least one fluos ea vat-magi, has a rine atom. the atomic weight of each substituted. halogen atom not exceeding 36, the proportion of propellant being from about 0.2 to about 0.0125 mm per 100 grams oi the composition, said propellant having a vap r pressure in the ran e from about to about 300 pounds per square inch gauge at 70 F. and having a solubility in water not exceeding about 32 cc. of gas to 100 grams or water at atmospheric pressure and 25 C.

2. A package comprising a pressure-tight container having a valve-controlled opening and containing a composition for use in producing a stable lather consisting essentially of a liquid mixture of an aqueous soap solution and a volatile propellant in liquid phase, the composition being confined in the container under the vapor pressure of the propellant, said soap solution comprising a solution which is non-gelling at room temperatures and which contains at least about 5% and not substantially exceeding about 30% by weight or soap, a substantial proportion of the soap in said soap solution comprising at least one soap selected from the group consisting of the soaps of potassium, sodium and the water soluble aliphatic amines, said propellant being a. halogenated alkane having not more than two carbon atoms and containing at least one fluorine atom, the atomic weight of each substituted halogen atom not exceeding 36, the proportion 01 propellant being from about 0.2 to about 0.0125 mole per 100 grams of the composition, said propellant having a vapor pressure in the range from about 5 to about 300 pounds per square inch gauge at 70 F. and having a solubility in water not exceeding about 32 cc. of gas to 100 grams of water at atmospheric pressure and 25 C.

3. A package according to claim 2, in which the propellant comprises 1,2 dichlor 1,1,2,2 tetrafiuorethane.

4. A package according to claim 2, in wh ah the propellant comprises dichlordifluormetzis re.

5. A package according to claim 2, in when the soap in the soap solution comprises a big reisaturated fatty acid triethanolamine soap and includes a lesser proportion 01' sodium soap.

6. A package according to claim 2, in which substantial proportion of the soap in the soap solution comprises triethanolamine stearate and the propellant comprises 1,2 dichlor 1,1,2,2 tetrafiuorethane.

7. A package according to claim 2, in which. a.

.substantial proportion of the soap in the soap solution comprises triethanolamine stearate and the propellant comprises trichlortrifiuorethane.

8. A package according to claim 2, in which a substantial proportion of the soap in the soap solution comprises triethanolamine stearate and the propellant comprises dichlordifluormethane.

9. A package according to claim 2, in which the soap in the soap solution comprises at least 30% triethanolamine stearate and the propellant comprises 1,2 dichlor 1,l,2,2 tetrafluorethane.

10. A' package according to claim 2, in which the soap in the soap solution comprises at least 30% triethanolamine stearate and thepr'vpellant comprises dichlordifluormethane.

11. A package comprising a pressure-tight container having a, valve-controlled opening and containing a composition for use in producing a stable lather consisting essentially of a liquid mixture of an aqueous soap solution and a volatile propellant in liquid phase, the composition being confined in the container under the vapor pressure of the propellant, said Wop solution comprising a solution which is non-gelling at room. temperatures and which contains at least about 5% and not substantially exceeding about 30% by weight oil soon, a substantial proportion of the soap in said soap solution comprising at least one soap selected from the' group consisting of the soaps of potassium, sodium and the water soluble aliphatic amines, said propellant comprising a mixture 01' dichlordifluormethane and 1,2 dichlor 1,1,2,2 tetrafluorethane, the proportion of propellant being from about 0.2 to about 0.0125 mole per grams of the composition.

12. A package comprising a pressure-tight container having a valve-controlled opening and containing a composition for use in producing a stable lather consisting essentially of a liquid mixture of an aqueous soap solution and a volatile propellant in liquid phase. the composition beingconfined in the container under the vapor pressure 01' the propellant, said soap solution comprising a solution which is non-gelling at room temperatures and which contains at least about 5% and not substantially exceeding about 30% by weight of soap, a substantial proportion of the soap in said soap solution comprising at least one soap selected from the group consisting 01' the soaps of potassium, sodium and the water-soluble aliphatic amines and including at least about 30% water soluble stearate soap, said propellant being a halogenated alkane having not more than two carbon atoms and containing at least one fluorine atom, the atomic weight of each substituted halogen atom not exceeding 36, the proportion of propellant being from about 0.2 to about 0.0125 mole per 100 grams of the composition, said propellant having a. vapor pressure in the range from about 1 to about 300 pounds per square inch gauge at I". and having a solubility in water not 7-:"'etiing about 82 cc. of gas to 100 grams of er at atmospheric pressure and 25 C.

A package comprising a pressure-tight elner having a valve-controlled opening and aining a composition for use in producing a. la lather consisting essentially of a liquid are of an aqueous soap solution and a volaziic propellant in liquid phase, the composition being confined in the container under the vapor ;;xressv.ire oi the propellant, said soap solution c-znprising a solution which is non-gelling at .\:n temperatures and which contains at least about 5% and not substantially exceeding about 2 0% by weight of soap, a substantial proportion of the soap in said soap solution comprising at least one soap selected from the group consisting of the higher saturated fatty acid soaps of potassium, sodium and the water-soluble aliphatic amines and including at least about 30% triethanolamine stearate soap. said propellant being a halogenated alkane having not more than two carbon atoms and containing at least one fluorine atom, the atomic weight oi each substituted halogen atom not exceeding 36. the proportion of propellant being from about 0.2 to about 0.0125 mole per 100 grams or the composition. said propellant having a vapor pressure in the range from about 5 to about 300 pounds per square inch gauge at 70 F. and having a solubility in water not exceeding about 32 cc. of gas to 100 grams oi water at atmospheric pressure and 25 C.

14. A package comprising a pressure-tight container having a valve-controlled openingand containing a composition fpr use in producing a if r 13 stable lather consisting essentially of a. liquid to about 18% by weight of soap, said propellant I mixture 01 an aqueous soap solution and a. volacomprising at least one compound selected from tile propellant in liquid phase, the composition the group consisting oi the substantially watcr- ,l.;.-. being confined in the container under the vapor insoluble fiuorinatcd-chlorinated ethanes and pressure oi the propellant, said soap solution 5 methanes in which all of the hydrogen atoms are comprising a solution which is non-gelling at replaced by chlorine and fluorine and in which room temperatures and which contains at least the number of fluorine atoms in the molecule at about 5% and not substantially exceeding about least equals the number of chlorine atoms, the p 30% by weight of soap, a substantial proportion proportion of propellant being from about .07 to h p in said soap solution comprising a about .025 mole per 100 grams of the composition, higher saturated fatty acid triethanolamine said propellant having a vapor pressure in the soap, said propellant being a halogenated alkane range of from about to about 65 pounds per having not more than two carbon atoms and consquare inch gauge at 70 F. taining at least one fluorine atom, the atomic 17. A package according to claim 16 in which weight of each substituted halogen atom not ex- 15 the soap solution contains about 10% by weight ceeding 36, the proportion of propellant being of soap. 3 from about 0.2 to about 0.0125 mole per 100 18. A package according to claim 16 in which f grams or the composition, said propellant having the soap in the soap solution comprises a higher a vapor pressure in the range from about 5 to saturated fatty acid triethanolamine soap.

about.300 pounds per square inch gauge at '10 20 19. A package according to claim 16 in which F. and having a solubility in water not exceeding the propellant consists of a mixture of dichlori about 32 cc. of gas to 100 grams of water at atdifiuormethane and 1,2 dichlor 1,1,2,2 tetrai mospheric pressure and C. fiuorethane.

15. A package comprising a pressure-tight 20. A package according to claim 16 in which container having a valve-controlled opening and 25 the propellant consists or a mixture of dichlordicontaining a composition for use in producing a fiuormethane and 1,2 dichlor l,1,2.2 tetrafluorei stable lather consisting essentially of a. liquid theme and in which the soap in the soap solution 1 mixture of an aqueous soap solution and a volacomprise a. higher saturated fatty acid tritile propellant in liquid phase, the composition ethanolamine soap and includes a lesser proporbeing confined in the container under the vapor tion of sodium soap. pressure of the propellant, said soap solution 21. A package comprising a pressure-tight/T comprising a solution which is non-gelling at container having a valve-controlled opening and room temperatures and which contains at least containing a composition for use in producing a about 5% and not substantially exceeding about stable lather consisting essentially of a liquid 30% by weight of soap, a substantial proportion mixture of an aqueous soap solution and a volaof the soap in said soap solution comprising at tile propellant in liquid phase, the composition least one soap selected from the group consistbeing confined in the container under the vapor ing or the higher saturated fatty acid soaps of pressure 01 the propellant, said composition conv potassium, sodium and the water-soluble alitaini-ng about 2.6% by weight of CClzFn, about 1 phatlc amines and including at least about 50 9;, 40 4.0% by weight of C2CI2F4 with the remainder of soluble stearate soap, not more than about 20% said composition being said soap solution, said of a refined petroleum oil having a viscosity in soap solution containing about 8.0% by weight the range from 30 to 70 seconds Saybolt at 100" of said solution of triethanolamine stearate and F., said propellant being a halogenated alkane 2% by weight of said solution of triethanolamine having not more than two carbon atoms and soap of cocoanut oil fatty acids. V containing at least one fluorine atom, the atomic weight 01 each substituted halogen atom not ex- JOSEPH SPITZER' ceeding 36, the proportion of propellant being IRVING REICH' '1 from about 0.2 to about 0.0125 mole per 100 NORMAN FINE- grams oi the composition, said propellant having l. a vapor pressure in the range from about 5 to References Cited in the file of this patent i about 300 pounds per square inch gauge at 70 UNITED STATES PATENTS 1. F. and having a solubility in water not exceeding Number Name t i about 32 cc. of gas to 100 grams of water at at- 1,392,750 th 3, 1937 m p i r r d 2 C. 2,0 7 Iddings Feb. 9, 1937 16- A pack ge c mpri ing a pr ss r -ti ht 2, 3 Getz Feb. 10, 1948 container having a valve-controlled opening and 2,524,590 3 t, 3, 1950 containing a composition for use in producing a i stable lather consisting essentially of a liquid mix- OTHER REFERENCES ture of an aqueous soap solution and a volatile Fulton, "Propellents for Low-pressure Liquepropellant in liquid phase, the composition being fled Gas Aerosols"; Ind. and Eng. Chem., April confined in the container under the vapor pres- 1948, pgs. 699-700. sureof the propellant, said soap solution com- Ind. 8: Eng. Chem, August 1949. vol. 41. No. 8.

7 prising a solution which is non-gelling at room. page 7A.

temperatures and which contains from about 5% 

1. A PACKAGE COMPRISING A PRESSURE-TIGHT CONTAINER HAVING A VALVE-CONTROLLED OPENING AND CONTAINING A COMPOSITION FOR USE IN PRODUCING A STABLE LATHER CONSISTING ESSENTIALLY OF A LIQUID MIXTURE OF AN AQUEOUS SOAP SOLUTION AND A VOLATILE PROPELLANT IN LIQUID PHASE, THE COMPOSITION BEING CONFINED IN THE CONTAINER UNDER THE VAPOR PRESSURE OF THE PROPELLANT, SAID SOAP SOLUTION COMPRISING A SOLUTION WHICH IS NON-GELLING AT ROOM TEMPERATURES AND WHICH CONTAINS AT LEAST ABOUT 5% AND NOT SUBSTANTIALLY EXCEEDING ABOUT 30% BY WEIGHT OF SOAP, SAID PROPELLANT BEING A HALOGENATED ALKANE HAVING NOT MORE THAN TWO CARBON ATOMS AND CONTAINING AT LEAST ONE FLUORINE ATOM, THE ATOMIC WEIGHT OF EACH SUBTITUTED HALOGEN ATOM NOT EXCEEDING 36, THE PROPORTION OF PROPELLANT BEING FROM ABOUT 0.2 TO ABOUT 0.0125 MOLE PER 100 GRAMS OF THE COMPOSITION, SAID PROPELLANT HAVING A VAPOR PRESSURE IN THE RANGE FROM ABOUT 5 TO ABOUT 350 POUNDS PER SQUARE INCH GAUGE AT 70* F. AND HAVING A SOLUBILITY IN WATER NOT EXCEEDING ABOUT 32 CC. OF GAS TO 100 GRAMS OF WATER AT ATMOSPHERIC PRESSURE AND 25* C. 